FLPs and Main Group Catalysis

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Chemical industry is the largest consumer of energy worldwide. The most common approach to addressing this problem involves energy-optimize chemical synthesis using catalysis to obtain high value-products from cheap starting materials. Commonly, industrial and academic research chemists use optimized catalytic methodologies aiming for energy efficiency. Indeed, catalysis is central to the manufacture of a myriad of products from pharmaceuticals to agro-chemicals, from polymers to foodstuffs. The vast majority of catalysts in use are based on precious metals, which are expensive, rare, toxic and are obtained with a large carbon footprint. Our research offers a fundamentally new and innovative approach to catalyst design and applications targeting the use of earth-abundant main group compounds. In 2006, we made the transformative discovery of that sterically frustrated Lewis pairs were able to activate H2. This led to FLP catalysts for simple and asymmetric hydrogenations, principally based on electrophilic boron-based FLPs. Moreover, we also showed FLPs could activate a variety of other small molecules, including olefins, alkynes, and the greenhouse gases, CO2, SO2 and N2O. At the same time, we explored and developed Lewis acid catalysis employing a variety of main group cations. Building on our world leading position in main group catalysis, the present research program focuses on advances that target new areas of application. Specifically, we target new, key reactions that are both of broad interest and high impact, Ultimately we hope to transform the notions of catalysis in the chemical community, demonstrating the wide utility of main group species in these efforts. Main group N2 Chemistry: In this proposal, we target a new strategy to capture and convert N2 using earth abundant, non-toxic main-group based compounds. While efforts to make NH3 will be considered direct access to high-value fine chemicals will also be targeted. C-F Bond Activation: We plan to develop strong main group Lewis acidic cation catalysts incorporating P(I), P(III) and P(V) cations, to target reactions of C-F bonds, providing access to libraries of new agrochemicals, drugs and materials derived from known compounds. C-H Bond Activation: In general, almost all strategies to C-H activation utilize directing groups and/or reactive metal catalysts. We plan to exploit the power of FLPs to provide metal-free strategies for catalytic routes to selective C-H derivatization. Main group metathesis: Olefin metathesis is a powerful synthetic tool in organic, polymer and materials chemistry. We have designed cationic P-based species targeting applications in olefin metathesis. In summary, our program targets new main group reagents for important stoichiometric and catalytic reactions. The longer term vision involves the introduction of green, efficient and economically viable main group catalyst technologies to chemical industry.